The invention relates to layered materials such as clay, which are intercalated by one or more block copolymer(s).
Over the last decade or so, the utility of inorganic nanoparticles as additives to enhance polymer performance has been well established. Ever since the seminal work conducted at Toyota Central Research Laboratories, polymer-clay nanocomposites have generated a lot of interest across industry. The unique physical properties of these nanocomposites have been explored by such varied industrial sectors as the automotive industry, the packaging industry, and plastics manufactures. These properties include improved mechanical properties, such as elastic modulus and tensile strength, thermal properties such as coefficient of linear thermal expansion and heat distortion temperature, barrier properties, such as oxygen and water vapor transmission rate, flammability resistance, ablation performance, solvent uptake, etc. Some of the related prior art is illustrated in U.S. Pat. Nos. 4,739,007; 4,810,734; 4,894,411; 5,102,948; 5,164,440; 5,16,460 5,248,720; 5,854,326; and 6,034,163.
In general, the physical property enhancements for these nanocomposites are achieved with less than 20 vol. % addition, and usually less than 10 vol. % addition of the inorganic phase, which is typically clay or organically modified clay. Although these enhancements appear to be a general phenomenon related to the nanoscale dispersion of the inorganic phase, the degree of property enhancement is not universal for all polymers. It has been postulated that the property enhancement is very much dependent on the morphology and degree of dispersion of the inorganic phase in the polymeric matrix.
The clays in the polymer-clay nanocomposites are ideally thought to have three structures (1) clay tactoids wherein the clay particles are in face-to-face aggregation with no organics inserted within the clay lattice, (2) intercalated clay wherein the clay lattice has been expanded to a thermodynamically defined equilibrium spacing due to the insertion of individual polymer chains, yet maintaining a long range order in the lattice; and (3) exfoliated clay wherein singular clay platelets are randomly suspended in the polymer, resulting from extensive penetration of the polymer into the clay lattice and its subsequent delamination. The greatest property enhancements of the polymer-clay nanocomposites are expected with the latter two structures mentioned herein above.
There has been considerable effort towards developing materials and methods for intercalation and/or exfoliation of clays and other layered inorganic materials. In addition to intercalation and/or exfoliation, the clay phase should also be rendered compatible with the polymer matrix in which they are distributed. The challenge in achieving these objectives arises from the fact that unmodified clay surfaces are hydrophilic, whereas vast number of thermoplastic polymers of technological importance are hydrophobic in nature. Although intercalation of clay with organic molecules can be obtained by various means, compatibilizing these intercalated clays in a polymer matrix for uniform distribution still poses considerable difficulty. In the industry, the clay suppliers normally provide just the intercalated clays and the end-users arc challenged to select materials and processes for compatibilizing these clays in the thermoplastics of their choice. This selection process involves trial and error at a considerable development cost to the end-users. Since clay intercalation and compatibilization in the matrix polymer usually involve at least two distinct materials, processes and sites, the overall cost of the product comprising the polymer-clay nanocomposite suffers.
A vast majority of intercalated clays are produced by interacting anionic clays with cationic surfactants including onium species such as ammonium (primary, secondary, tertiary, and quaternary), phosphonium, or sulfonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines and sulfides. These onium ions can cause intercalation in the clay through ion exchange with the metal cations present in the clay lattice for charge balance. However, these surfactant molecules may degrade during subsequent melt-processing, placing severe limitation on the processing temperature and the choice of the matrix polymer. Moreover, the surfactant intercalation is usually carried out in the presence of water, which needs to be removed by a subsequent drying step.
Intercalation of clay with a polymer, as opposed to a low molecular weight surfactant, is also known in the art. There are two major intercalation approaches that are generally usedxe2x80x94intercalation of a suitable monomer followed by polymerization (known as in-situ polymerization, see A. Okada et Al., Polym Prep., Vol. 28, 447, 1987) or monomer/polymer intercalation from solution. Polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP) and polyethylene oxide (PEO) have been used to intercalate the clay platelets with marginal success. As described by Levy et. al, in xe2x80x9cInterlayer adsorption of polyvinylpyrrolidone on montmorillonitexe2x80x9d, Journal of Colloid and Interface Science, Vol 50 (3), 442, 1975, attempts were made to sorb PVP between the monoionic montmorillonite clay platelets by successive washes with absolute ethanol, and then attempting to sorb the PVP by contacting it with 1% PVP/ethanol/water solutions, with varying amounts of water. Only the Na-montmorillonite expanded beyond 20 xc3x85 basal spacing, after contacting with PVP/ethanol/water solution. The work by Greenland, xe2x80x9cAdsorption of polyvinyl alcohol by montmorrilonitexe2x80x9d, Journal of Colloid Science, Vol. 18, 647-664 (1963) discloses that sorption of PVA on the montmorrilonite was dependent on the concentration of PVA in the solution. It was found that sorption was effective only at polymer concentrations of the order of 1% by weight of the polymer. No further effort was made towards commercialization since it would be limited by the drying of the dilute intercalated layered materials. In a recent work by Richard Vaia et.al., xe2x80x9cNew Polymer Electrolyte Nanocomposites: Melt intercalation of polyethyleneoxide in mica type silicatesxe2x80x9d, Adv. Materials, 7(2), 154-156, 1995, PEO was intercalated into Na-montmorillonite and Li- montmorillonite by heating to 80xc2x0 C. for 2-6 hours to achieve a d-spacing of 17.7xc2x0xc3x85. The extent of intercalation observed was identical to that obtained from solution (V. Mehrotra, E. P. Giannelis, Solid State Commun., 77, 155, 1991). Other, recent work (U.S. Pat. No. 5,804,613) has dealt with sorption of monomeric organic compound having at least one carbonyl functionality selected from a group consisting of carboxylic acids and salts thereof, polycarboxylic acids and salts thereof, aldehydes, ketones and mixtures thereof. Similarly U.S. Pat. No. 5,880,197 discusses the use of an intercalating monomer that contains an amine or amide functionality or mixtures thereof. In both these patents, and other patents issued to the same group, the intercalation is performed at very dilute clay concentrations in a medium such as water, leading to a necessary and costly drying step, prior to melt-processing.
In order to further facilitate delamination and prevent reaggregation of the clay particles, these intercalated clays are required to be compatible with the matrix polymer in which they are to be incorporated. This can be achieved through the careful selection and incorporation of compatibilizing or coupling agents, which consist of a portion which bonds to the surface of the clay and another portion which bonds or interacts favorably with the matrix polymer. Compatibility between the matrix polymer and the clay particles ensures a favorable interaction which promotes the dispersion of the intercalated clay in the matrix polymer. Effective compatibilzation leads to a homogenous dispersion of the clay particles in the typically hydrophobic matrix polymer and/or an improved percentage of exfoliated or delaminated clay. Typical agents known in the art include general classes of materials such as organosilane, organozirconate and organotitanate coupling agents. However, the choice of the compatibilizing agent is very much dependent on the matrix polymer as well as the specific component used to intercalate the clay, since the compatibilizer has to act as a link between the two.
A survey of the art, makes it clear that there is a lack of general guideline for the selection of the intercalating and compatibilizing agents for a specific matrix polymer and clay combination. Even if one can identify these two necessary components through trial and error, they are usually incorporated as two separate entities, usually in the presence of water followed by drying, in a batch process and finally combined at a separate site with the matrix polymer during melt-processing of the nanocomposite. Such a complex process obviously adds to the cost of development and manufacturing of the final product comprising such a nanocomposite. There is a critical need in the art for a comprehensive strategy for the development of better materials and processes to overcome some of the aforementioned drawbacks.
Imaging elements such as photographic elements usually comprise a flexible thermoplastic base on which is coated the imaging material such as the photosensitive material. The thermoplastic base is usually made of polymers derived from the polyester family such as polyethylene terephthalate(PET), polyethylene naphthalate(PEN) and cellulose triacetate(TAC). Films for color and black and white photography, and motion picture print film are examples of imaging media comprising such flexible plastic bases in roll form. TAC has attributes of high transparency and curl resistance after processing but poor mechanical strength. PET on the other hand has excellent mechanical strength and manufacturability but undesirable post process curl. The two former attributes make PET more amenable to film thinning, enabling the ability to have more frames for the same length of film. Thinning of the film however causes loss in mechanical strength. The stiffness will drop as approximately the cube root of the thickness of the film. Also a photosensitive material coated on the base in a hydrophilic gelatin vehicle will shrink and curl towards the emulsion when dry. There is hence a need for a base that is thinner yet stiff enough to resist this stress due contraction forces. Films may also be subjected to excursions to high temperatures during use. Hence, a transparent film base that has dimensional stability at high temperatures due to its higher heat capacity is also highly desirable.
It is an object of the invention to provide an intercalated clay. It is a further object of the invention to provide an intercalated clay which further comprises a component compatible with a matrix polymer in which the clay can be dispersed. It is an even further object of the invention to provide an article comprising a matrix polymer and an intercalated clay wherein said intercalated clay comprises a matrix compatible component.
These and other objects of the invention are accomplished by providing an intercalated clay comprising a clay intercalated with a block copolymer wherein said block copolymer comprises a hydrophilic block capable of intercalating said clay. The present invention further includes an article comprising a matrix polymer and clay wherein said clay is intercalated with a block copolymer, wherein said block copolymer comprises a hydrophilic block capable of intercalating said clay and a matrix compatible block compatible with said matrix polymer. The clay may be a clay intercalated with an amphiphilic block copolymer. The amphiphilic block copolymer of the invention may also comprise a hydrophilic block capable of intercalating the clay. The block copolymer may further comprise a block that does not intercalate the clay or a block that is an oleophilic polymer.